Crystal structure of dimethyl 1,4,6,9-tetraphenylhexahydro-3H-2,7,3,5-(epimethanetriyliminomethanetriyl)cyclopenta[b]pyridine-3,7(2H)-dicarboxylate, C38H34N2O4

Yin-Xin Wang; Si-Qi Geng; Jia-Rui Qin; Wen-Li Zhang; Qi-Di Zhong

doi:10.1515/ncrs-2022-0038

Open Access Published by De Gruyter (O) April 4, 2022

Crystal structure of dimethyl 1,4,6,9-tetraphenylhexahydro-3H-2,7,3,5-(epimethanetriyliminomethanetriyl)cyclopenta[b]pyridine-3,7(2H)-dicarboxylate, C₃₈H₃₄N₂O₄

Yin-Xin Wang , Si-Qi Geng , Jia-Rui Qin , Wen-Li Zhang and Qi-Di Zhong

From the journal Zeitschrift für Kristallographie - New Crystal Structures

https://doi.org/10.1515/ncrs-2022-0038

Abstract

C₃₈H₃₄N₂O₄, triclinic, P 1 ‾ (no. 2), a = 11.1158(19) Å, b = 11.302(2) Å, c = 12.634(2) Å, α = 72.109(2)°, β = 77.410(2)°, γ = 82.648(3)°, V = 1362.4(5) Å³, Z = 2, R_gt(F) = 0.0473, wR_ref(F²) = 0.1738, T = 296 K.

CCDC no.: 2143423

The molecular structure is shown in Figure. Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal:	Colourless block
Size:	0.18 × 0.16 × 0.15 mm
Wavelength:	Mo Kα radiation (0.71073 Å)
μ:	0.09 mm⁻¹
Diffractometer, scan mode:	Bruker APEX-II, φ and ω
θ_max, completeness:	27.5°, 99%
N(hkl)_measured, N(hkl)_unique, R_int:	9220, 6596, 0.016
Criterion for I_obs, N(hkl)_gt:	I_obs > 2σ(I_obs), 5121
N(param)_refined:	399
Programs:	Bruker [1], SHELX [2, 3]

Table 2:

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²).

Atom	x	y	z	U_iso*/U_eq
O1	0.43060 (10)	0.33694 (12)	0.25888 (11)	0.0486 (3)
O2	0.41268 (10)	0.44641 (12)	0.38234 (10)	0.0492 (3)
O3	1.07900 (12)	0.56210 (16)	0.16452 (12)	0.0692 (5)
O4	0.98680 (11)	0.54287 (13)	0.34253 (10)	0.0536 (4)
N1	0.71403 (11)	0.63020 (11)	0.21005 (10)	0.0307 (3)
N2	0.74671 (10)	0.30828 (11)	0.35398 (10)	0.0302 (3)
C1	1.04233 (16)	0.17146 (17)	0.15810 (18)	0.0514 (5)
H1	1.030837	0.194130	0.083546	0.062*
C2	1.11000 (19)	0.06188 (19)	0.1988 (2)	0.0656 (6)
H2	1.142688	0.011300	0.152270	0.079*
C3	1.12887 (18)	0.0278 (2)	0.3081 (2)	0.0717 (7)
H3	1.174450	−0.045941	0.336023	0.086*
C4	1.07979 (17)	0.1037 (2)	0.3770 (2)	0.0623 (6)
H4	1.092537	0.080719	0.451179	0.075*
C5	1.01157 (15)	0.21393 (18)	0.33553 (16)	0.0491 (4)
H5	0.979509	0.264685	0.382042	0.059*
C6	0.99089 (13)	0.24892 (15)	0.22523 (14)	0.0396 (4)
C7	0.92002 (13)	0.36777 (14)	0.17107 (12)	0.0348 (3)
H7	0.972447	0.405381	0.097995	0.042*
C8	0.88342 (12)	0.47221 (14)	0.22896 (12)	0.0319 (3)
C9	0.81264 (13)	0.57168 (14)	0.14110 (11)	0.0324 (3)
H9	0.867530	0.632637	0.085875	0.039*
C10	0.75604 (13)	0.49305 (15)	0.08349 (12)	0.0345 (3)
H10	0.785948	0.514756	0.001409	0.041*
C11	0.79379 (13)	0.35783 (14)	0.14407 (12)	0.0337 (3)
H11	0.798609	0.302025	0.097085	0.040*
C12	0.69248 (12)	0.32287 (13)	0.25424 (11)	0.0306 (3)
H12	0.650261	0.249372	0.260418	0.037*
C13	0.60202 (12)	0.44331 (13)	0.24500 (11)	0.0299 (3)
C14	0.66390 (12)	0.52218 (13)	0.29893 (11)	0.0284 (3)
H14	0.607939	0.544653	0.362330	0.034*
C15	0.77867 (12)	0.43449 (13)	0.33603 (11)	0.0289 (3)
H15	0.800076	0.445776	0.403415	0.035*
C16	0.74712 (13)	0.73169 (13)	0.23860 (12)	0.0322 (3)
C17	0.73080 (15)	0.73823 (16)	0.34895 (14)	0.0416 (4)
H17	0.696713	0.673274	0.409280	0.050*
C18	0.76563 (18)	0.84230 (18)	0.36893 (16)	0.0548 (5)
H18	0.753605	0.846053	0.443050	0.066*
C19	0.81710 (17)	0.93929 (18)	0.28242 (17)	0.0558 (5)
H19	0.841967	1.007025	0.297458	0.067*
C20	0.83132 (18)	0.93455 (17)	0.17267 (17)	0.0546 (5)
H20	0.865425	1.000005	0.112908	0.065*
C21	0.79526 (16)	0.83324 (16)	0.15077 (14)	0.0454 (4)
H21	0.803199	0.832644	0.076115	0.054*
C22	0.61473 (13)	0.50144 (14)	0.11513 (12)	0.0337 (3)
H22	0.585652	0.441173	0.086356	0.040*
C23	0.54602 (15)	0.62529 (15)	0.07012 (13)	0.0390 (4)
C24	0.60661 (18)	0.72672 (19)	−0.00652 (17)	0.0575 (5)
H24	0.691986	0.719685	−0.029116	0.069*
C25	0.5418 (2)	0.8377 (2)	−0.0495 (2)	0.0786 (7)
H25	0.584379	0.904547	−0.099898	0.094*
C26	0.4155 (2)	0.8509 (2)	−0.0191 (2)	0.0747 (7)
H26	0.372717	0.926176	−0.047961	0.090*
C27	0.3534 (2)	0.7514 (2)	0.05451 (18)	0.0615 (5)
H27	0.267785	0.758896	0.075170	0.074*
C28	0.41778 (16)	0.63963 (18)	0.09822 (14)	0.0470 (4)
H28	0.374321	0.572757	0.147426	0.056*
C29	0.68045 (12)	0.24302 (13)	0.46162 (12)	0.0292 (3)
C30	0.65222 (14)	0.29058 (15)	0.55398 (13)	0.0376 (3)
H30	0.675482	0.369469	0.546073	0.045*
C31	0.58983 (16)	0.22175 (18)	0.65769 (14)	0.0476 (4)
H31	0.572065	0.254901	0.718665	0.057*
C32	0.55378 (16)	0.10502 (18)	0.67175 (15)	0.0500 (4)
H32	0.510939	0.059688	0.741309	0.060*
C33	0.58199 (16)	0.05666 (16)	0.58164 (16)	0.0488 (4)
H33	0.558509	−0.022423	0.590529	0.059*
C34	0.64494 (15)	0.12373 (15)	0.47752 (14)	0.0406 (4)
H34	0.663776	0.088962	0.417553	0.049*
C35	0.30507 (16)	0.3035 (2)	0.30004 (18)	0.0573 (5)
H35A	0.250371	0.373478	0.271723	0.086*
H35B	0.288198	0.279568	0.381335	0.086*
H35C	0.292657	0.234958	0.274590	0.086*
C36	0.47204 (13)	0.41176 (14)	0.30550 (12)	0.0328 (3)
C37	1.0814 (2)	0.6115 (3)	0.3553 (2)	0.0775 (7)
H37A	1.160365	0.566957	0.343338	0.116*
H37B	1.063779	0.620733	0.430278	0.116*
H37C	1.082978	0.692274	0.300708	0.116*
C38	0.99411 (14)	0.52876 (15)	0.24132 (13)	0.0377 (3)

Source of material

Preparation of the 1,4-diaryl-1,4-dihydropyridine-3-carboxylic acid photoreactive raw materials was performed by a literature method [4]: aniline (0.5 mmol), ethyl propiolate (0.5 mmol) and 4-methylcinnamaldehyde (0.5 mmol); piperazine (0.25 mmol) and p-toluenesulfonic acid (0.02 mmol) used as catalysts, and 20 mL of 1,2-dichloroethane (20 mL) were mixed. The mixture was heated to reflux for 12 h to obtain 1-phenyl-4-(4-methyl-phenyl)-1,4-dihydroethylpyridine-3-carboxylate. The 1-phenyl-4-(4-methyl-phenyl)-1,4-dihydroethylpyridine-3-carboxylate (0.5 mmol) obtained in the first step was placed near a blue LED (365 nm) for a photoreaction for 3 h [5]. The product was obtained by column chromatography eluting with petroleum ether and ethyl acetate 10:1. The resulting solution was evaporated to get some colorless crystals.

Experimental details

All hydrogen atoms were placed in the calculated positions.

Comment

Cage dimer 4-aryl-1,4-dihydropyridines have a wide range of biological activities, such as anti-HIV and as an antimultidrug resistance modulator [6], [7], [8]. The caged dimeric compound similar to the title compound has also been reported, which is obtained by a dimerization by photoreaction. However, the two pyridine rings in the title compound present a special angle, which may be of interest for the study of new functional caged compounds.

In the molecules forming the title crystal structure, the tricyclic structure formed by oxazinoquinoline structure is not in one plane. The dihedral angle of the phenyl ring formed by C23–28 and the phenyl ring formed by C6–C1 is 57°. The dihedral angle between the phenyl ring formed by C16–18 and the phenyl ring formed by C29–34 is 33.322 Å, close to a right angle. Several important bond angle data are involved as follows C2–C1–C6 = 121.9(2) Å, C36–O1–C35 = 117.56(13) Å, C16–N1–C14 = 120.10(11) Å. The bond lengths and angles are in the expected ranges [9, 10].

Corresponding author: Wen-Li Zhang, Comprehensive Testing and Analytical Center, North China University of Science and Technology, 063210 Caofeidian District, Tangshan, P. R. China, E-mail: dianj@163.com

Funding source: Hebei Provincial Natural Science Foundation of China

Award Identifier / Grant number: C2020209081

Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: This work is supported by The Project Supported by Hebei Provincial Natural Science Foundation of China (C2020209081).
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Received: 2022-01-21

Accepted: 2022-03-11

Published Online: 2022-04-04

Published in Print: 2022-06-27

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